CN103794786A - Preparation method of doped lithium manganous silicate-carbon composite positive electrode material - Google Patents
Preparation method of doped lithium manganous silicate-carbon composite positive electrode material Download PDFInfo
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- CN103794786A CN103794786A CN201410057859.6A CN201410057859A CN103794786A CN 103794786 A CN103794786 A CN 103794786A CN 201410057859 A CN201410057859 A CN 201410057859A CN 103794786 A CN103794786 A CN 103794786A
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- lithium
- gadolinium
- doped lithium
- positive electrode
- carbon composite
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 title abstract 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 26
- ADXGYIOOUFNERA-UHFFFAOYSA-N gadolinium vanadium Chemical compound [V][Gd] ADXGYIOOUFNERA-UHFFFAOYSA-N 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 229920001400 block copolymer Polymers 0.000 claims abstract description 9
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 polyethylene-ethylene Polymers 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910015645 LiMn Inorganic materials 0.000 claims abstract description 6
- IIQWDCSKVVOBGH-UHFFFAOYSA-N [Mg].[Yb] Chemical compound [Mg].[Yb] IIQWDCSKVVOBGH-UHFFFAOYSA-N 0.000 claims abstract description 5
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 claims description 25
- 239000010405 anode material Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 claims description 10
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 4
- ZEEDCGIEVPGBCZ-UHFFFAOYSA-N [Li].[Mn].P(O)(O)(O)=O Chemical compound [Li].[Mn].P(O)(O)(O)=O ZEEDCGIEVPGBCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229940097206 manganese citrate Drugs 0.000 claims description 4
- 235000014872 manganese citrate Nutrition 0.000 claims description 4
- 239000011564 manganese citrate Substances 0.000 claims description 4
- 239000000320 mechanical mixture Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a doped lithium manganous silicate-carbon composite positive electrode material. Ytterbium magnesium doped lithium manganese phosphate has the chemical formula of LiMn(1-x-y)VxGdySiO4, wherein x is equal to 0.12-0.15, and y is equal to 0.03-0.045. The preparation method mainly comprises the following steps: (1) preparing gadolinium vanadium doped lithium manganous silicate; and (2) mixing polyethylene-ethylene glycol block copolymer and cellulose acetate, dispersing the mixture into isopropanol so as to form a conductive carbon dispersion liquid, mixing a gadolinium vanadium doped lithium manganous silicate precursor and the conductive carbon dispersion liquid, carrying out ball milling on the mixed material, drying, and sintering, thereby obtaining the gadolinium vanadium doped lithium manganous silicate-carbon composite positive electrode material. The gadolinium vanadium doped lithium manganous silicate-carbon composite positive electrode material prepared by the invention improves the electron conductivity and lithium ion migration rate by adding a rare earth element Gd and a metal element V into lithium manganous silicate for modification, and the surface of the gadolinium vanadium doped lithium manganous silicate-carbon composite positive electrode material is coated with a carbon coating network by adopting an organic carbon source, and further the conductive performance and the cycle stability of the gadolinium vanadium doped lithium manganous silicate-carbon composite positive electrode material are improved.
Description
Affiliated technical field
The present invention relates to a kind of preparation method of doping type manganese silicate of lithium-carbon composite anode material.
Background technology
Along with developing rapidly of battery industry, in order to solve the problems such as useful life, energy density, self discharge or the quality of battery, various types of batteries are there are.At present, there is the advantages such as energy density is high, long service life, quality is light, self discharge is little due to lithium battery, now become the first-selected power supply of the portable set such as communication apparatus, notebook computer, and also started to be applied in the medium-and-large-sized equipment such as electric motor car, national defence.
Be applied to the main positive electrode of electrokinetic cell, comprised stratiform transition metal oxide (LiMO
2), olivine-type LiFePO4 (LiFePO
4) and lithium manganate having spinel structure (LiMn
2o
4).There are respectively different defects in above-mentioned three kinds of materials: 1. stratiform transition metal oxide overcharging resisting performance is poor; 2. the theoretical capacity of olivine-type LiFePO4 is lower, voltage platform is lower, energy density is less, conductivity is poor; 3. lithium manganate having spinel structure high-temperature behavior is poor.Therefore, high, the Heat stability is good of exploitation specific capacity, cheap chargeable lithium battery positive electrode become one of the study hotspot in lithium battery field.
Polyanion type positive electrode has caused people's extensive concern as anode material for lithium-ion batteries of new generation, particularly be considered to the most promising silicate anodal material and there is lot of advantages: the lithium that 1. every 1mol silicate can deintercalation 2mol in theory, gram volume is up to 330mAh/g; 2. silicon content is on earth only second to oxygen, very abundant, so silicate anodal material is expected to become real inexpensive anode material of lithium battery; 3. between silicon and oxygen, pass through very strong covalent bonds, in the deintercalation process of lithium ion, be difficult for producing oxygen, thus very safe, there is good high-temperature behavior.In addition, the advantage such as silicate anodal material also has good cycle performance, higher specific energy, thereby be expected to become the anode material for lithium-ion batteries that has application prospect most of future generation after LiFePO4.
Summary of the invention
The invention provides a kind of preparation method of doping type manganese silicate of lithium-carbon composite anode material, the positive electrode that uses the method to prepare, had compared with height ratio capacity and longer useful life.
To achieve these goals, the preparation method of a kind of doping type manganese silicate of lithium-carbon composite anode material provided by the invention, the method comprises the steps:
(1) prepare the manganese silicate of lithium that gadolinium vanadium adulterates
The chemical formula of this ytterbium magnesium doping phosphoric acid manganese lithium is LiMn
1-x-yv
xgd
ysiO
4wherein: x=0.12-0.15, y=0.03-0.045, take lithium acetate, manganese citrate, vanadic oxide, gadolinium nitrate, silester according to the mole of the Li in above-mentioned chemical formula, Mn, V, Gd, Si, mechanical mixture, after ball milling 6-10h, is scattered in deionized water, the complexing agent citric acid that to add with the mol ratio of lithium acetate be 1:1.2-1.5, obtains mixed solution;
Use is equipped with pressurized nozzles spray dryer and is dried, and this mixed solution is fed in to 1:1 (mol) CO/CO
2mixture purges in batch (-type) converter, in 1-2h, temperature is warmed up to 700-800 ℃ gradually, then, keeping 5-7h, is then cooled to ambient temperature at 40-50min, obtains the manganese silicate of lithium of gadolinium vanadium doping;
(2) carbon is coated
Polyethylene-ethylene glycol the block copolymer that is 1:1-2 by mass ratio and cellulose acetate are distributed in isopropyl alcohol after mixing, form conductive carbon dispersion liquid, wherein the mass ratio of isopropyl alcohol and polyethylene-ethylene glycol block copolymer and cellulose acetate mixture is 10:2-3;
By the manganese silicate of lithium presoma of gadolinium vanadium doping and above-mentioned conductive carbon dispersion liquid according to the manganese silicate of lithium of gadolinium vanadium doping with conductive carbon mixture weight than 100: the ratio of 2-3 is mixed to get compound, by compound in planetary ball mill with rotating speed 400-500r/min ball milling 10-15h; After material after ball milling is dry, be placed in 1:1 (mol) CO/CO
2mixture purges in batch (-type) converter, in 800-900 ℃ of roasting temperature 8-12h, obtains gadolinium vanadium doping manganese silicate of lithium-carbon composite anode material.
Gadolinium vanadium doping manganese silicate of lithium-carbon composite anode material prepared by the present invention, in manganese silicate of lithium, doped with rare-earth elements Gd and metallic element V modification are to improve electronic conductivity and lithium ion migration rate, and adopt organic carbon source at the coated network of its coated with carbon, further improve its electric conductivity and cyclical stability.Therefore this composite material, when for lithium ion battery, has higher specific capacity and longer useful life.
Embodiment
Embodiment mono-
The chemical formula of the ytterbium magnesium doping phosphoric acid manganese lithium of preparation is LiMn
0.85v
0.12gd
0.03siO
4. take lithium acetate, manganese citrate, vanadic oxide, gadolinium nitrate, silester according to the mole of the Li in above-mentioned chemical formula, Mn, V, Gd, Si, mechanical mixture, after ball milling 6h, be scattered in deionized water, the complexing agent citric acid that to add with the mol ratio of lithium acetate be 1:1.2, obtains mixed solution.
Use is equipped with pressurized nozzles spray dryer and is dried, and this mixed solution is fed in to 1:1 (mol) CO/CO
2mixture purges in batch (-type) converter, in 1h, temperature is warmed up to 700 ℃ gradually, then, keeping 7h, is then cooled to ambient temperature at 40min, obtains the manganese silicate of lithium of gadolinium vanadium doping.
Polyethylene-ethylene glycol the block copolymer that is 1:1 by mass ratio and cellulose acetate are distributed in isopropyl alcohol after mixing, and form conductive carbon dispersion liquid, and wherein the mass ratio of isopropyl alcohol and polyethylene-ethylene glycol block copolymer and cellulose acetate mixture is 10:2.
The manganese silicate of lithium presoma of gadolinium vanadium doping and above-mentioned conductive carbon dispersion liquid are mixed to get to compound with conductive carbon mixture weight than the ratio of 100: 2 according to the manganese silicate of lithium of gadolinium vanadium doping, by compound in planetary ball mill with rotating speed 400r/min ball milling 15h; After material after ball milling is dry, be placed in 1:1 (mol) CO/CO
2mixture purges in batch (-type) converter, in 800 ℃ of roasting temperature 12h, obtains gadolinium vanadium doping manganese silicate of lithium-carbon composite anode material.
Embodiment bis-
The chemical formula of the ytterbium magnesium doping phosphoric acid manganese lithium of preparation is LiMn
0.805v
0.15gd
0.045siO
4. take lithium acetate, manganese citrate, vanadic oxide, gadolinium nitrate, silester according to the mole of the Li in above-mentioned chemical formula, Mn, V, Gd, Si, mechanical mixture, after ball milling 10h, be scattered in deionized water, the complexing agent citric acid that to add with the mol ratio of lithium acetate be 1:1.5, obtains mixed solution.
Use is equipped with pressurized nozzles spray dryer and is dried, and this mixed solution is fed in to 1:1 (mol) CO/CO
2mixture purges in batch (-type) converter, in 2h, temperature is warmed up to 800 ℃ gradually, then, keeping 5h, is then cooled to ambient temperature at 50min, obtains the manganese silicate of lithium of gadolinium vanadium doping.
Polyethylene-ethylene glycol the block copolymer that is 1:2 by mass ratio and cellulose acetate are distributed in isopropyl alcohol after mixing, and form conductive carbon dispersion liquid, and wherein the mass ratio of isopropyl alcohol and polyethylene-ethylene glycol block copolymer and cellulose acetate mixture is 10:3.
The manganese silicate of lithium presoma of gadolinium vanadium doping and above-mentioned conductive carbon dispersion liquid are mixed to get to compound with conductive carbon mixture weight than the ratio of 100: 3 according to the manganese silicate of lithium of gadolinium vanadium doping, by compound in planetary ball mill with rotating speed 500r/min ball milling 10h; After material after ball milling is dry, be placed in 1:1 (mol) CO/CO
2mixture purges in batch (-type) converter, in 900 ℃ of roasting temperature 8h, obtains gadolinium vanadium doping manganese silicate of lithium-carbon composite anode material.
Comparative example
Accurately take 200g nano silicon, 600g ferrous oxalate, 687g lithium acetate, 40g glucose, add 2L deionized water and stirring 1h.Transferred in ball mill, ball milling 10h under the rotating speed of 500r/min, takes out the slurry that obtains mixing.Then, spray drying granulation under 200 ℃ of conditions, obtains the presoma of uniform-spherical particle.The presoma of having sprayed is placed in to stove, and with nitrogen, as protective atmosphere, nitrogen flow 6L/min, rises to 650 ℃ with the heating rate of 5 ℃/min by furnace temperature, and then sintering 12h at 650 ℃ to be cooledly ground 400 mesh sieves by product to room temperature, obtained Li
2feSiO
4/ C positive electrode.
Above-described embodiment one, two and comparative example products therefrom are mixed with the mass ratio ratio of 80: 10: 10 with conductive black and adhesive Kynoar, be made into the button-shaped test battery of same specification.Reference electrode is lithium metal, and electrolyte is 1mol/l LiPF
6eC/DEC/DMC (volume ratio 1: 1: 1).Be at 25 ℃, to carry out electric performance test at probe temperature, experimental technique is: with 0.05C rate charge-discharge 5 times, carry out charge-discharge test with 0.1C multiplying power again, charging/discharging voltage is 2.0-4.5V, after tested compared with the product of this embodiment mono-and two material and comparative example, first charge-discharge capacity has improved 34-39%, and bring up to more than 35% useful life.
Claims (1)
1. a preparation method for doping type manganese silicate of lithium-carbon composite anode material, the method comprises the steps:
(1) prepare the manganese silicate of lithium that gadolinium vanadium adulterates
The chemical formula of this ytterbium magnesium doping phosphoric acid manganese lithium is LiMn
1-x-yv
xgd
ysiO
4wherein: x=0.12-0.15, y=0.03-0.045, take lithium acetate, manganese citrate, vanadic oxide, gadolinium nitrate, silester according to the mole of the Li in above-mentioned chemical formula, Mn, V, Gd, Si, mechanical mixture, after ball milling 6-10h, is scattered in deionized water, the complexing agent citric acid that to add with the mol ratio of lithium acetate be 1:1.2-1.5, obtains mixed solution;
Use is equipped with pressurized nozzles spray dryer and is dried, and this mixed solution is fed in to 1:1 (mol) CO/CO
2mixture purges in batch (-type) converter, in 1-2h, temperature is warmed up to 700-800 ℃ gradually, then, keeping 5-7h, is then cooled to ambient temperature at 40-50min, obtains the manganese silicate of lithium of gadolinium vanadium doping;
(2) carbon is coated
Polyethylene-ethylene glycol the block copolymer that is 1:1-2 by mass ratio and cellulose acetate are distributed in isopropyl alcohol after mixing, form conductive carbon dispersion liquid, wherein the mass ratio of isopropyl alcohol and polyethylene-ethylene glycol block copolymer and cellulose acetate mixture is 10:2-3;
By the manganese silicate of lithium presoma of gadolinium vanadium doping and above-mentioned conductive carbon dispersion liquid according to the manganese silicate of lithium of gadolinium vanadium doping with conductive carbon mixture weight than 100: the ratio of 2-3 is mixed to get compound, by compound in planetary ball mill with rotating speed 400-500r/min ball milling 10-15h; After material after ball milling is dry, be placed in 1:1 (mol) CO/CO
2mixture purges in batch (-type) converter, in 800-900 ℃ of roasting temperature 8-12h, obtains gadolinium vanadium doping manganese silicate of lithium-carbon composite anode material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115394998A (en) * | 2022-09-29 | 2022-11-25 | 大连工业大学 | Application of molybdenum-doped nano cellulose-based manganese lithium silicate as positive electrode active material in lithium ion battery |
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|---|---|---|---|---|
| CN101504994A (en) * | 2009-03-04 | 2009-08-12 | 张贵萍 | Lithium manganese phosphate or lithium manganese silicate power cell, positive and negative pole manufacturing method thereof |
| EP2416412A1 (en) * | 2009-03-31 | 2012-02-08 | Mitsubishi Heavy Industries, Ltd. | Lithium ion secondary battery and battery system |
| CN103342369A (en) * | 2013-06-08 | 2013-10-09 | 合肥国轩高科动力能源股份公司 | Method for synthesizing silicate cathode material by taking rice husk as raw material |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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